Copper complexation of rosarin: formation of bis-copper rosarin and mono-copper linear tridipyrrin complexes

A novel rosarin di-Cu complex 2Cu-1 and a linear six-pyrrolic mono-copper complex 1Cu-1 were synthesized using rosarin as the ligand. The molecular conformations of these complexes were confirmed by X-ray crystallography. The optical study of 1Cu-1 indicated NIR-II absorption due to the long six-pyrrolic ligand and the ICT effect. The 2Cu-1 complex exhibited a very narrow electronic reduction-oxidation gap of 0.50 eV, attributed to the antiaromatic characteristics of the rosarin ring. The first HER study of the di-copper rosarin complex 2Cu-1 indicated that the multi-metal poly-pyrrolic complexes are promising molecular hydrogen evolution reaction catalysts.